The Use of Halide Charged Interleaves for Treatment of Iron Gall Ink
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The use of halide charged interleaves for treatment of iron gall ink damaged papers Véronique Rouchon, Maroussia Duranton, Oulfa Belhadj, Marthe Bastier-Deroches, Valéria Duplat, Charlotte Walbert, Birgit Hansen To cite this version: Véronique Rouchon, Maroussia Duranton, Oulfa Belhadj, Marthe Bastier-Deroches, Valéria Du- plat, et al.. The use of halide charged interleaves for treatment of iron gall ink dam- aged papers. Polymer Degradation and Stability, Elsevier, 2013, 98, pp.1339 - 1347. 10.1016/j.polymdegradstab.2013.03.028. hal-01435102 HAL Id: hal-01435102 https://hal.archives-ouvertes.fr/hal-01435102 Submitted on 13 Jan 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. 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Authors requiring further information regarding Elsevier’s archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/authorsrights Author's personal copy Polymer Degradation and Stability 98 (2013) 1339e1347 Contents lists available at SciVerse ScienceDirect Polymer Degradation and Stability journal homepage: www.elsevier.com/locate/polydegstab The use of halide charged interleaves for treatment of iron gall ink damaged papers Véronique Rouchon a,*, Maroussia Duranton a, Oulfa Belhadj a, Marthe Bastier-Deroches a, Valéria Duplat a,b, Charlotte Walbert a, Birgit Vinther Hansen b a Centre de Recherche sur la Conservation des Collections, Muséum national d’Histoire naturelle, Centre national de la recherche scientifique, Ministère de la Culture et de la Communication, USR3224, CP21, 36 rue Geoffroy-Saint-Hilaire, 75005 Paris, France b The Royal Library, Preservation Dept., P.O. Box 2149, DK-1016 Copenhagen, Denmark article info abstract Article history: In certain conditions, iron gall inks induce substantial damages on cellulosic supports. Existing curative Received 14 December 2012 treatments necessitate the immersion of the documents in aqueous solutions. This implies several un- Received in revised form desirable side effects: mechanical stress of the most damaged papers, substantial colour changes, and a 4 March 2013 drastic modification of the paper/ink composition. This work investigated an alternative treatment that Accepted 31 March 2013 consists in compressing the document between two interleaves that are charged with active compounds. Available online 17 April 2013 When this operation is operated in moist conditions, active compounds may migrate from the interleaves to the document, and thus achieve the treatment of the paper. As high humidity conditions may addi- Keywords: fi Halide tionally induce some migration of iron and acidic compounds out of the ink line, it rst appeared Iron gall ink necessary to research humidity conditions which minimize these undesirable migrations. This investi- Paper gation was performed on a set of 53 original manuscripts and led us to consider that a relative humidity Treatment of 80% was quite reasonable. The second part of the paper deals with the evaluation of interleaving Interleaf treatment efficiency. It was performed on laboratory samples, using several types of antioxidant halide Humidity salts (NaCl, NaBr, CaBr2) (halides are known to act as radical scavengers). These compounds were tested separately or in combination with calcium carbonate as an alkaline buffer. The samples were made of Whatman paper that was preliminary impregnated with iron gall ink. It has shown that a charge of 2% calcium carbonate in the interleaves has no impact on the treatment efficiency, which mainly depends upon the concentration of salts, the contact pressure and the duration of the treatment. Elemental measurements show that the mobility of the salts is much higher than that of iron, suggesting the possibility to find optimum treatment conditions that minimize the iron migration risk while achieving an effective migration of halides. Ó 2013 Elsevier Ltd. All rights reserved. 1. Introduction acid), and gum arabic as a binder. They also contain large quantities of iron and present low pH values (in the range 1.5e3). As a result, 1.1. Iron gall inks: a major threat for western archives they can cause a major degradation of the cellulosic carrier [2,3]. This degradation results from the superimposition of two types In western countries, iron gall inks were used on a significant of phenomena: the first is mainly physical and corresponds to the part of archival patrimony dating from medieval times up to the migration of acidic and iron rich by-products out of the ink line [4]. beginning of the 20th century. These inks are made from a mixture It is, among others, provoked by exposure to high humidity con- [1] of iron salts (for example iron II sulphate heptahydrate), gall ditions [5]. The second is mainly chemical, and occurs in the paper nuts extracts (rich in polyphenolic carboxylic acids, such as gallic fibres that are in contact with the ink. This chemical degradation includes cellulose hydrolysis promoted by the acidity of the ink, and cellulose oxidation, catalysed by iron II and possibly imparted * Corresponding author. Tel.: þ33 1 4079 5303; fax: þ33 1 4079 5312. to hydroxyl radicals produced via Fenton mechanisms [6].Itwas E-mail addresses: [email protected] (V. Rouchon), [email protected] recently demonstrated that oxidation was the driving force of cel- (M. Duranton), [email protected] (O. Belhadj), [email protected] (M. Bastier-Deroches), [email protected] (V. Duplat), cha.walbert@ lulose depolymerization induced by iron gall inks [7]. This suggests gmail.com (C. Walbert), [email protected] (B.V. Hansen). that the oxidized cellulose reorganizes through chain scissions with 0141-3910/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.polymdegradstab.2013.03.028 Author's personal copy 1340 V. Rouchon et al. / Polymer Degradation and Stability 98 (2013) 1339e1347 a kinetic that is much faster than that of acidic hydrolysis. In 1.4. Aim of the study addition, it was shown that gallic acid was favouring oxidation phenomena [6], probably because of its high ability to reduce iron This study aims to investigate halide based interleaving treat- III into iron II [8,9]. ments using moderate conditions. Halide salts were chosen for this purpose and used separately or in combination with calcium car- 1.2. Available treatments and their side effects bonate. In addition to the aforementioned sodium bromide (NaBr), calcium bromide (CaBr2) was chosen because of the ability of cal- A significant amount of work has been realized in the last de- cium to bind carboxylic groups on cellulose chains [31], which may cades to find chemical treatments capable of limiting iron gall ink improve the treatment efficacy. Sodium chloride (NaCl) was addi- damages. The calcium phytate process proposed in the 90’s [10] has tionally included because chloride, already highlighted as an effi- been the most widely tested [11]. Although its efficiency is well cient anti-oxidant [21,24], is smaller than bromide, and thus may established, this treatment is rarely used, mainly because it re- migrate more easily. quires immersions in aqueous solutions, which provokes drastic When manuscripts are exposed to high humidity conditions, modifications of the paper’s appearance, of its chemical composi- brown ink compounds may additionally migrate out of the ink line tion [12e14] and mechanical damages for brittle papers [15]. These and through the paper. These unaesthetic brown halos are often side effects are often found unacceptable. accompanied by a substantial migration of iron [5] and should For several decades, halides are known to decompose hydrogen therefore be considered as potentially detrimental to the conser- peroxide [16]. This property is probably correlated to their ability vation of the carrier. We thus dedicated the first part of this work to to react with hydroxyl radicals thus acting as radical scavengers the risk assessment of these migration phenomena. [17e19]. In the 2000’s, a major effort was paid for the testing of The second part of this research deals with the monitoring of the non-aqueous treatments using halide products as anti-oxidants. treatment. Several types of interleaves and several types of treat- Several studies report the efficiency of bromide and chloride ment were implemented in order to identify the most effective compounds prepared in several organic solvents [20e25]. These ones. results are encouraging. However, in all these studies, halide based treatments were implemented after a conventional aqueous 2. Experimental deacidification, meaning that the global treatment remains water based with all relating side effects. 2.1. Methodology to evaluate the risk of ink migration related to high humidity exposure 1.3. Interleaving techniques The risk of ink migration was evaluated on a set of 53 original Interleaving techniques consist in placing the document in manuscripts dating from 1818 to 1896, and originating from the contact with an interleaving paper impregnated with some active south of France. These manuscripts were formally chosen to study compounds. The ensemble is then pressed and kept at high relative the migration risk of aqueous treatments and are therefore humidity (RH) for several days.